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At least 37 records · Page 2

Sensitized Liquid Hydrazine Detonation Studies

Vapor-phase hydrazine (N2H4) is known to be very sensitive to detonation while liquid hydrazine is very insensitive to detonation, theoretically requiring extremely high pressures to induce initiation. A review of literature on solid and liquid explosives shows that when pure explosive substances are infiltrated with gas cavities, voids, and/or different phase contaminants, the energy or shock pressure necessary to induce detonation can decrease by an order of magnitude. Tests were conducted with liquid hydrazine in a modified card-gap configuration. Sensitization was attempted by bubbling helium gas through and/or suspending ceramic microspheres in the liquid. The hydrazine was subjected to the shock pressure from a 2 lb (0.9 kg) Composition C-4 explosive charge. The hydrazine was contained in a 4 in. (10.2 cm) diameter stainless steel cylinder with a 122 in(sup 3) (2 L) volume and sealed with a polyethylene cap. Blast pressures from the events were recorded by 63 high speed pressure transducers located on three radial legs extending from 4 to 115 ft (1.2 to 35.1 in) from ground zero. Comparison of the neat hydrazine and water baseline tests with the "sensitized" hydrazine tests indicates the liquid hydrazine did not detonate under these conditions.

Rathgeber, K. A.

Catalytic Decomposition of Propellant Hydrazines, N-Nitrosodimethylamine, and N-Nitrodimethylamine

Remediation of propellant hydrazine spills, waste treatment, or cleanup of water contaminated with these propellants and/or their oxidation products is a subject of great concern for safety and the environment. Current remediation technologies typically employ oxidative methods, such as chlorination or ozonation. Methylated hydrazines, in particular 1,1-dimethythydrazine (UDMH) and to some degree monomethy1hydrazine (MMH), form N-Nitrosodimethylamine (NDMA) and N-Nitrodimethylamine (DMNM) during oxidation. These compounds are highly toxic and may persist if oxidative conditions are not sufficiently harsh. Since NDMA and DMNM may also be formed from exposure of MMH or UDMH to air, a need exists for a method that will remediate hydrazine, MMH, UDMH, NDMA, and DMNM. In this work, aqueous solutions of propellant hydrazines, NDMA, and DMNM were found to degrade by catalytic reduction with nickel-aluminum (Ni-Al) alloy under basic conditions. The reaction is based upon dissolution of At from Ni-Al alloy in aqueous media to form aluminum ion and hydrogen gas; and the resultant finely divided nickel catalyzes reduction of the hydrazine, nitrosoamine, or nitroamine by the hydrogen produced. Greater than 99 percent of hydrazine, MMH, UDMH, NDMA, and DMNM in aqueous solutions were degraded under laboratory conditions when reacted with Ni-Al alloy. UDMH was identified as an intermediate reduction product of NDMA and DNNM. NDMA and UDMH were identified as intermediate reduction products of DMNM. Control experiments without nickel showed no degradation of hydrazine, MMH or UDMH, while NDMA and DMNM were reduced to UDMH. Spill pillows containing Ni-Al alloy and solid sodium hydroxide were also found effective in absorption and degradation of UDMH. The application of chemical reduction as a means to propellant hydrazines, NDMA, and DMNM spill remediation, waste treatment, and water decontamination appears highly attractive.

Greene, Ben

Hydrazine Conservation for the Dawn Spacecraft Operations at the Dwarf Planet Ceres

Dawn is a low-thrust interplanetary spacecraft currently orbiting the dwarf planet Ceres. After successfully completing its Vesta and Ceres prime missions, Dawn is now in its extended mission, continuously exploring Ceres. After losing the second reaction wheel assembly at the end of the Vesta mission, the feasibility of the Ceres mission was at risk due to the potentially significant increase in hydrazine consumption from using only the reaction control system thrusters. This paper summarizes the intense, collaborative efforts undertaken by the project to conserve hydrazine prior to Vesta departure, during cruise to Ceres, and throughout the Ceres mission. The project’s efforts in minimizing the number of turns are discussed. A special emphasis is given to describing various efforts taken by the Attitude Control Subsystem team in an attempt to reduce hydrazine consumption. These efforts include: changing default slew rates, control gain tuning, changing nadir pointing strategy with Ahead Cross Nadir pointing, hybrid control implementation using hydrazine based thrusters and two remaining reaction wheels, optimal science turn location analysis, and reaction wheel angular momentum management strategies for reducing the number of momentum unloadings. In addition to the Attitude Control Subsystem team’s efforts, the Mission Design and Navigation team’s efforts taken in designing hydrazine friendly orbit transfers are discussed. The trade study performed collaboratively by the Attitude Control Subsystem team and the Science Operations Support Team in choosing hydrazine friendly off-nadir targets is also discussed. Various simulation results are presented and compared against actual flight data obtained. Lastly, remaining hydrazine status at the end of the prime Ceres mission and the hydrazine management planning for the extended mission are discussed.

Salami, Mana

The X-Irradiation of Hydrazine and 1,1- Dimethylhydrazine

Hydrazine and 1,1-dimethylhydrazine were radiolyzed at room temperature by using about 1 gram of liquid or 1/2 to 2 liters of vapor at room-temperature vapor pressure. A tungsten-target X-ray source operating at 300 kilovolts and 6 to 8 milliamperes (0.1 to 1.0 A) was used at intensities of 1 times 10 (sup 2) to 1 times 10 (sup 3) roentgens per minute to give total doses of 4.1 rads to 2.3 times 10 (sup 6) rads. The amounts of decomposition were dependent on total dose and independent of dose rate. In the case of hydrazine vapor, the decomposition was also directly related to surface area. There was a lesser surface effect with liquid hydrazine, but this variable was not studied for 1,1-dimethylhydrazine. The order of decreasing sensitivity to X-radiation is as follows: hydrazine vapor, 1,1-dimethylhydrazine vapor, 1,1-dimethylhydrazine liquid, and hydrazine liquid. The decomposition products of hydrazine were nitrogen, hydrogen, ammonia, and unidentified products. The same products plus methylamine, dimethylamine, and hydrazine were found from the decomposition of 1,1-dimethylhydrazine. In addition, the 1,1-dimethylhydrazine underwent post-irradiation changes. Values for G (number of molecules of sample decomposed per 100 electronvolts of absorbed energy) of the order of 10 (sup 6) suggest that the vapor-phase decompositions are chain reactions.

X-RAY IRRADIATION

Modulating Concentration Of Hydrazine Vapor To Aid Detection

Three techniques, flow modulation, filament modulation, and reactive-filter modulation developed to obtain selective response to hydrazine or to methyl hydrazines from photoionization detector. Implemented in portable selective hydrazine detectors, useful where continuous or rapid, repetitive quantitative measurements of concentrations of vapors of these toxic substances required. Measure concentration of gaseous hydrazines in presence of other gases like cyclohexane, chlorofluorocarbons, and ammonia. Produce modulated signal, amplitude and phase indicating amount of hydrazine, monomethyl hydrazine, or 1,1-dimethyl hydrazine present in mixture. Used with such other detectors as electrochemical cells.

Stetter, Joseph R.

Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.

Meagher, Nancy E.

Detection of hydrazine (H) and (MMH) using cyranose E-nose

The Cyranose electronic nose (e-nose) has been used for the first time to detect hydrazine (H) and monomethyl hydrazine (MMH). The concentrations of hydrazine chosen in this study were 52 ppm (parts per million), 18 ppm, and 1.1 ppm and the concentrations of MMH was 14 ppm and 1 ppm. The Cyranose E-nose has detected hydrazine of 52 ppm and 18 ppm with a good response. The response of the E-Nose for 1.1 ppm hydrazine was insignificant. The response of E-Nose for 14 ppm MMH was significant and 1 ppm MMH was reasonably identifiable. The Cyranose E-Nose may be used to detect hydrazine and MMH with concentrations of at least 18 ppm and 1 ppm, respectively.

cyranose

Explosive decomposition of hydrazine by rapid compression of a gas volume

In the present investigation of the initiation mechanism and the explosion mode of hydrazine decomposition, a 20 cm-long column of liquid hydrazine was accelerated into a column of gaseous nitrogen, from which it was separated by a thin Teflon diaphragm, in a close-ended cylindrical chamber. Video data obtained reveal the formation of a froth generated by the acceleration of hydrazine into nitrogen at the liquid hydrazine-gaseous nitrogen interface. The explosive hydrazine decomposition had as its initiation mechanism the formation of a froth at a critical temperature; the explosion mode of hydrazine is a confined thermal runaway reaction.

Bunker, R. L.

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Coyne, L. M.

Occupational safety considerations with hydrazine fuels

A simple pharmacokinetic model and a specially designed dermal vapor exposure chamber which provides respiratory protection were used to determine the rate of penetration of hydrazine and 1,1-dimethylhydrazine (UDMH) vapor through the skin of rats. Parameters for the pharmacokinetic model were determined from intravenous and inhalation exposure data. The model was then used to estimate the skin permeation coefficient for hydrazine or UDMH vapor from the dermal-vapor exposure data. This analysis indicates that UDMH vapor has a relatively high permeability through skin (0.7 cm/hr), a value somewhat higher than was obtained for hydrazine by the same procedure (0.09 cm/hr). Based on these skin permeability results, a skin-only vapor exposure limit giving protection equivalent to the inhalation Threshold Limit Value (TLV) could be calculated. The current TLV's for UDMH and hydrazine are 0.5 and 0.1 ppm, respectively. The corresponding skin-only TLV equivalents, for personnel wearing respiratory protection, are 32 ppm for UDMH and 48 ppm for hydrazine. Should the proposed lowering to the TLV's for these compounds to 0.01 ppm be adopted, the equivalent skin-only TLV's would become 0.64 ppm for UDMH and 4.8 for hydrazine.

Clewell, H. J.

Prototype development and test results of a continuous ambient air monitoring system for hydrazine at the 10 ppb level

A Hydrazine Vapor Area Monitor (HVAM) system is currently being field tested as a detector for the presence of hydrazine in ambient air. The MDA/Polymetron Hydrazine Analyzer has been incorporated within the HVAM system as the core detector. This analyzer is a three-electrode liquid analyzer typically used in boiler feed water applications. The HVAM system incorporates a dual-phase sample collection/transport method which simultaneously pulls ambient air samples containing hydrazine and a very dilute sulfuric acid solution (0.0001 M) down a length of 1/4 inch outside diameter (OD) tubing from a remote site to the analyzer. The hydrazine-laden dilute acid stream is separated from the air and the pH is adjusted by addition of a dilute caustic solution to a pH greater than 10.2 prior to analysis. Both the dilute acid and caustic used by the HVAM are continuously generated during system operation on an "as needed" basis by mixing a metered amount of concentrated acid/base with dilution water. All of the waste water generated by the analyzer is purified for reuse by Barnstead ion-exchange cartridges so that the entire system minimizes the generation of waste materials. The pumping of all liquid streams and mixing of the caustic solution and dilution water with the incoming sample are done by a single pump motor fitted with the appropriate mix of peristaltic pump heads. The signal to noise (S/N) ratio of the analyzer has been enhanced by adding a stirrer in the MDA liquid cell to provide mixing normally generated by the high liquid flow rate designed by the manufacturer. An onboard microprocessor continuously monitors liquid levels, sample vacuum, and liquid leak sensors, as well as handles communications and other system functions (such as shut down should system malfunctions or errors occur). The overall system response of the HVAM can be automatically checked at regular intervals by measuring the analyzer response to a metered amount of calibration standard injected into the dilute acid stream. The HVAM system provides two measurement ranges (threshold limit value (TLV): 10 to 1000 parts per billion (ppb)/LEAK: 100 ppb to 10 parts per million (ppm)). The LEAK range is created by dilution of the sulfuric acid/hydrazine liquid sample with pure water. This dual range capability permits the analyzer to quantify ambient air samples whose hydrazine concentrations range from 10 ppb to as high as 10 ppm. The laboratory and field prototypes have demonstrated total system response times on the order of 10 to 12 minutes for samples ranging from 10 to 900 ppb in the lLV mode and is greater than 2 minutes for samples ranging from 100 to 1300 ppb in the LEAK mode. Service intervals of over 3 months have been demonstrated for continuous 24 hour/day, 7 day/week usage. The HVAM is made up of a purged cabinet that contains power supplies, RS422 signal transmission capabilities, a UPS, an on-site warning system, and a Line Replaceable Unit (LRU). The LRU includes all of the liquid flow system, the analyzer, the control/data system microprocessor and assorted flow and liquid-level sensors. The LRU is mounted on a track slide system so it can be serviced inplace or totally removed and quickly exchanged with another calibrated unit, thus minimizing analyzer downtime. Once an LRU is removed from an analyzer enclosure, it can be brought to a laboratory facility for complete calibration and periodic maintenance.

Meneghelli, Barry

A Hydrazine Leak Sensor Based on Chemically Reactive Thermistors

Leaks in the hydrazine supply system of the Shuttle APU can result in hydrazine ignition and fire in the aft compartment of the Shuttle. Indication of the location of a leak could provide valuable information required for operational decisions. WSTF has developed a small, single use sensor for detection of hydrazine leaks. The sensor is composed of a thermistor bead coated with copper(II) oxide (CuO) dispersed in a clay or alumina binder. The CuO-coated thermistor is one of a pair of closely located thermistors, the other being a reference. On exposure to hydrazine the CuO reacts exothermically with the hydrazine and increases the temperature of the coated-thermistor by several degrees. The temperature rise is sensed by a resistive bridge circuit and an alarm registered by data acquisition software. Responses of this sensor to humidity changes, hydrazine concentration, binder characteristics, distance from a liquid leak, and ambient pressure levels as well as application of this sensor concept to other fluids are presented.

Davis, Dennis D.

Mobility Spectrometer Studies on Hydrazine and Ammonia Detection

An airborne vapor analyzer for detecting sub- to low- parts-per-million (ppm) hydrazine in the presence of higher concentration levels of ammonia has been under development for the Orion program. The detector is based on ambient pressure ionization and ion mobility characterization. The detector encompasses: 1) a membrane inlet to exclude particulate and aerosols from the analyzer inlet; 2) a method to separate hydrazine from ammonia which would otherwise lead to loss of calibration and quantitative accuracy for the hydrazine determination; and 3) response and quantitative determinations for both hydrazine and ammonia. Laboratory studies were made to explore some of these features including mobility measurements mindful of power, size, and weight issues. The study recommended the use of a mobility spectrometer of traditional design with a reagent gas and equipped with an inlet transfer line of bonded phase fused silica tube. The inlet transfer line provided gas phase separation of neutrals of ammonia from hydrazine at 50 C simplifying significantly the ionization chemistry that underlies response in a mobility spectrometer. Performance of the analyzer was acceptable between ranges of 30 to 80 C for both the pre-fractionation column and the drift tube. An inlet comprised of a combined membrane with valve-less injector allowed high speed quantitative determination of ammonia and hydrazine without cross reactivity from common metabolites such as alcohols, esters, and aldehydes. Preliminary test results and some of the design features are discussed.

Niu, William

Crowd-Sourced Technology Challenge for Improving Visual Color Detection of Hydrazine and Monomethylhydrazine Vapors in Spacecraft Environments

NASA currently uses a visual colorimetric detection method for potential hydrazine, monomethylhydrazine (MMH), or unsymmetrical dimethylhydrazine (UDMH) contamination in the International Space Station. Astronauts exposed to propellants or their residues during extravehicular activities may transfer contaminants into the airlock. The colorimetric detection method employs the Contamination Detection Kit (CDK), which uses a potassium tetrachloroaurate redox reaction with the propellant hydrazine vapors and a color comparison card to determine airborne concentrations. Seeking ideas for improvement, the NASA Tournament Lab (NTL) crowdsourced a way to tackle the challenge of detecting hydrazine and MMH vapors using colorimetric detection methods. This Rid the Rocket competition drew over 200 participants and 20 submissions from around the world proposing innovative ways to develop a new chemical colorimetric detection method for hydrazine and MMH vapors on spacecraft. Using a phased approach to evaluate contestants, NASA eventually narrowed the field to five finalists from the United States, Romania, Taiwan, and India. Concept papers and hardware submissions were judged on feasibility, creativity, and ability to detect hydrazine and MMH vapors before being sent to the NASA White Sands Test Facility for laboratory evaluation. Finalists employed variations of sampling methods and color-detection chemistry using a variety of sampling pumps and indicator pads or solutions—including those employing potassium or hydrogen tetrachloroaurate, para -dimethylaminobenzaldehyde (PDAB), and modifiers including sodium metasilicate and cetyltrimethylammonium bromide—to enhance gold nanoparticle formation and surface plasmon resonance (SPR) resulting in visual blue to purple color development. This paper presents a summary of the crowdsourced submissions and results of laboratory testing.

Crowd-Sourced

Sustained load crack growth design data for Ti-6Al-4V titanium alloy tanks containing hydrazine

Results are presented for an experimental study intended to provide sustained load crack growth (SLCG) data for Ti-6Al-4V titanium alloy tanks containing MIL-P-26536 hydrazine and refined hydrazine. Fracture mechanics data on crack growth threshold for heat-treated forgings, aged and unaged welds, and aged and unaged heat-affected zones (HAZ) are presented. All tests were made on uniaxially loaded fracture mechanics specimens involving part-through cracks, and an electrical discharge machined notch was used to start the crack. Fracture mechanics design curves of crack growth threshold stress intensity versus temperature are obtained for the temperature range 40-71 C. Major conclusions are that extreme susceptibility to SLCG in hydrazine is a universal property of unaged weld metal in Ti-6Al-4V titanium alloy of normal interstitial content, and that aging both weld metal and HAZ at 510 C for 4 hr after welding completely removes all susceptibility to SLCG induced by hydrazine, with less susceptibility to SLCG in refined hydrazine.

Lewis, J. C.

Auto-ignition of hydrazine by engineering materials

Hydrazine, being a monopropellant, can explode and/or detonate in contact with some materials. This has been generally recognized and minimized by testing the compatibility of engineering materials with hydrazine at ambient temperature. Very limited tests have been done at elevated temperatures. To assess the potential hazard of hydrazine leakage into a propulsion compartment (boattail), autoignition characteristics of hydrazine were tested on 18 engineering materials and coatings at temperatures of 120 C to over 330 C. Furthermore, since hydrazine can decompose violently in nitrogen or helium, common purging cannot assure safety. Therefore tests were also made in nitrogen. Detonations occurred on contact with five materials in air. Similar tests in nitrogen did not lead to ignition.

Perkins, J. H.

Test program to demonstrate the stability of hydrazine in propellant tanks

A 24-month coupon test program to evaluate the decomposition of propellant tanks is reported. The propellant fuel evaluated was monopropellant-grade hydrazine (N2H4), which is normally a colorless, fuming, corrosive, strongly reducing liquid. The degree of hydrazine decomposition was determined by means of chemical analyses of the liquid and evolved gases at the end of the test program. The experimental rates of hydrazine decomposition were determined to be within acceptable limits. The propellant tank materials and material combinations were not degraded by a 2-year exposure to hydrazine propellant. This was verified using change-of-weight determinations and microscopic examination of the specimen surface before and after exposure, and by posttest chemical analyses of hydrazine liquid for residual metal content.

Moran, C. M.

Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

Kilduff, Jan E.